Square planar complexes of nickel(II), palladium(II) and
platinum(II) with 1-(2-hydroxyphenyl)-3,5-diphenylformazan
Citation for published version (APA):
Balt, S., Meuldijk, J., & Renkema, W. E. (1980). Square planar complexes of nickel(II), palladium(II) and
platinum(II) with 1-(2-hydroxyphenyl)-3,5-diphenylformazan. Transition Metal Chemistry, 5(6), 357-361.
https://doi.org/10.1007/BF01396960
DOI:
10.1007/BF01396960
Document status and date:
Published: 01/01/1980
Document Version:
Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers)
Please check the document version of this publication:
• A submitted manuscript is the version of the article upon submission and before peer-review. There can be
important differences between the submitted version and the official published version of record. People
interested in the research are advised to contact the author for the final version of the publication, or visit the
DOI to the publisher's website.
• The final author version and the galley proof are versions of the publication after peer review.
• The final published version features the final layout of the paper including the volume, issue and page
numbers.
Link to publication
General rights
Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain
• You may freely distribute the URL identifying the publication in the public portal.
If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license above, please follow below link for the End User Agreement:
www.tue.nl/taverne
Take down policy
If you believe that this document breaches copyright please contact us at:
openaccess@tue.nl
providing details and we will investigate your claim.
• . . S " "11
Transition Met. Chem. 5, 357-361 (198111 1-( 2-Hvdroxvphenvl )-3,5-diphcnylformazan complexe, ol Ni ,Pd tt and Pttt 357
11187 (1971). - ("''F. E. Mabbs, J. K. Porter and W. E. Small, J. lnorg. Nucl. Chem., 35, 3219 (19731.- (17~ H. Yokoi, M. Sai and T. lsobe, Bull. (_Twin, Soc. Jpn., 45, 2189 { 1972). - ~ts~ 1. M, Proctor, B. J. Hathaway and P. Nichols, J. Chem. soc. A. 1678 (19681. - ~1,,~ B. J. Hathaway, D. E. Billing. P. Nichols and 1. NI. Proctor, J. Chenl. Soc. A, 319 (1969). - (:(" J. Schneider and A. V. Zelewskv, Heh'. ('him. Acta., 48. 1529 (1965).
(2h D. Kivelson and R. Neimann, J. Chem. Ph.vs., 35, 146 (1961). - q22j R. S. Giordano and R. D. Bereman. J. Am. Chem. Soc., 9(>, 1019 (I974).
T M C 350
Square Planar Complexes of Nickel(II), Palladium(II) and Platinum(II)
with 1-(2-Hydroxyphenyl)-3,5-diphenylformazan
Sijbe Bait*, Jan Meuldijk and Willem E. Renkema
D e p a r t m e n t of Inorganic Chemistry of the Free University, De Boelelaan 1083, 1081 H V A m s t e r d a m , The Netherlands
Summary
A novel series of formazan c o m p l e x e s of general formula F o M L [HeFo = 1-(2-hydroxyphenyl)-3,5-diphenylformazan: M = Ni u, Pd u or P0t: L = N H 3, py and PhsP] are described. The formazan nickel(ll) system shows linkage isomerism: one isomer, A, contains an unusual f i v e - m e n % e r e d formazan che- late ring, whereas the other, isomer B, has the usual six-mem- bered ring. ~SC n.m.r., u.v. and i.r. spectra are presented and interpreted. F r o m these the palladium and platinum con> plexes appear to contain the s i x - m e m b e r e d ring of the B type isomer.
Introduction
The versatility of forn3azans as complex folming agents is amply d e m o n s t r a t e d by the kinetic studies of the reaction of 1-(2-carboxyphenyl)-3,5-diphenylformazan (11 with cop- p e r ( l l ) and nickel(lI) ~11 and the reaction of l-(2qD, droxy- phenyl)-3,5-diphenylformazan (21 with copper(ll)C!. For the latter reaction, intermediates have been proposed on the basis of the m e d i u m d e p e n d e n c e of the rate law, hut isolation of these c o m p o t m d s in a pure form was unsuccessfuP ~.
We now report the isolation of an intermediate m the reac- tion between formazan (2) and nickel(II). The final product (3) of this reaction has the usual formazan coordination~ak Intermediate (4) has a f i v e - m e m b e r e d forrnazan chelate ring(SL
In addition, palladium(I!) and platinum(lI) compounds of coordination type (3) are reported, These c o m p o u n d s were prepared to serve as model c o m p o u n d s | o r studies of solvation effects on the ligand exchange kinetics of Reaction (1 l:
F o M X + Y ---, F o M Y + X ( 1 )
HeFo = formazan (2)
These c o m p o u n d s provide an opportunity to separate specific and general solwltion effects in ligand exchange "'~ mechanisms. Further physico-chemical properties of the com- plexes are also reported, i.e. i,r. u.v. and ~3C n.m.r, spectra.
* Auihor to whom all correspondence should be directed. O \.'erlag ('henfie. (imbll. 1)-(~94(I \VeinhcmL 19811
In this report the following numbering of the atoms in the formazans will be used:
, ~ - -c : N, II ~]l
(41
~ 2 ? N - % O
' , _ \
35: I t N a N5
The hydroxyphenylformazan (2) will be denoted as H2Fo. C o m p o u n d s with methyl substituted in the rings lII and V at the 4(para) position will be designed as H2"CH~-Fo or H g C H 3 - F o respectively.
Results and Discussion
Mixing of an ammoniacal solution of nickel(l l) pe.chlorate in ethanol-water with a solution of l-(2-hydroxyphenyl)-3,5- diphenylformazan in the same solvent immediately produces a dark product which can be separated into purple and green components by colunm chromatography. The two components have the same analytical composition: FoNiNH3, but different properties, as illustrated by the absorption spectra (Figure 1) from which it is clear that two isomers are involved. In the following discussion we denote the purple isomer as A and the green one as B. It was found that the relative amount of isomer A in the product could be increased by increasing the ammonia concentration in the reaction mixtt, re.
A similar complex of isomer type A and with formula FoNipy (py = pyridine) could be prepared by pyridine exchange with the a m m o n i a complex. Complexes of type B were formed in high yield when the unidentate ligand was O34( ~-4285,'S( )~( )612-( )357 $( )2.5()/0
358 S. Ball, J. Meuldi k and W. E. R c n k c n l a Transition Met. C h c m . 5. 357-361 (19811) 10" E 0 ¢ 7, ",~ 0 6 a ~, o4 > o~ / - ' - , , - \ / ', '\
~6oo ~o6oo ~6oo
~(cm-') •
Figure I. U.v. vis spectra o f the two isomeric fornls of amincJl-(2- (hydroxyphcnyl)-3.5-diphenylformazanatolnickcl(lI) in 51):S{Iv/v E t O H : H,O. Thc broken line refers to thc A isomer, the solid line Io the B isomer. a d d e d after t h e n i c k e l ( l l ) salt a n d t h e f o r m a z a n h a d b e e n a d d e d t o g e t h e r in s o l u t i o n : in a d d i t i o n to F o N i N l l ~ we w e r e a b l e to p r e p a r e in t h i s w a v c o m p l e x e s w i t h c o m p o s i t i o n F o N i p y a n d F o N i t p p ( t p p = t r i p h e n y l p h o s p h i n e ) , all o f t y p e B. P a l l a d i u m ( l l ) a n d p l a t i n u m ( I I ) c o m p l e x e s o f f o r m u l a F o M X ( M = Pd o r Pt: X = N H 3, py o r t p p ) c o u l d also be p r e p a r e d , b u t o n l y in o n e i s o m e r i c f o r m . A n x - r a y s t r u c t u r e d e t e r m i n a t i o n s h o w e d t h e n i c k e l c o m - p l e x F o N i N I t ~ ( i s o m e r B) to h a v e t h e u s u a l ~al c o o r d i n a t i o n o f t h e f o r m a z a n in a s i x - m e m b e r e d r i n g . (31. w h e r e a s i s o m e r A h a s a less o b v i o u s s t r u c t u r e ~5~ (4) w i t h a f i v e - m e m b e r c d f o r m a - z a n r i n g , as p r e v i o u s l y o b s e r v e d for t h e c o p p e r ( 1 ) c o m p l c x o f m o l e c u l a r d i p h e n y l f o r r n a z a n lvl. L~C n . m . r , spectra T h e t3C r e s o n a n c e s f o r t h e v a r i o u s c o m p o u n d s s t u d i e d a r e listed in T a b l e 1. A s s i g n m e n t s a n d c o n c l u s i o n s a r e p r e s e n t e d s e p a r a t e l y f o r t h e l i g a n d s a n d t h e m e t a l c o m p l e x e s . F o r m a z a n s
The assignment of the resonances of the phenyI rings I1l and
V
follow from a comparison of the spectrum of the formazanH2Fo
(2)
with spectra of its methyl-substituted derivatives, the
effect of methyl substitution obeying the general pattern
observed for aromatic azo and imine compounds~SL The L~C
resonances belonging to phenyl group
I
were assigned by using t h e o b s e r v a t i o n e~' m~ t h a t t h e e f f e c t o f s u b s t i t u e n t s o n t h e ]~C c h e m i c a l s h i f t s o f b e n z e n e r i n g s g e n e r a l l y f o l l o w s t h e s a m e q u a l i t a t i v e p a t t e r n i r r e s p e c t i v e o f t h e o t h e r s u b s t i t u c n t s p r e - s e n t . U s i n g t h i s c o n c e p t , a c o m p a r i s o n o f t h e f o r m a z a n s p e c t r a w i t h t h o s e o f p h e n o l , b e n z e n e ~]~ a n d t r u n s - a z o b e n z e n e ts~ y i e l d e d t h e d e s i r e d r i n g a s s i g n m e n t s . S o m e c o n c l u s i o n s a b o u t t h e s t r u c t u r e o f t h e f o r m a z a n s in d i c h l o r o m e t h a n e s o l u t i o n e m e r g e : t h e i d e n t i t y o f t h e r e s o n a n c e s o f t h e r i n g s 1 a n d V in t r i p h e n y l f o r m a z a n i n d i c a t e s t h e w e l l - k n o w n ~L' ~)~ t a u t o m c r i c e q u i l i b r i u m b e t w e e n a l o c a t i o n o f t h e a c i d i c p r o t o n o n N~ a n d N5. F o r t h e h y d r o x y p h e n y l f o r m a z a n (2), t h e t a u t o m e r i c e q u i l i b r i u m , if it e x i s t s , m u s t b e c l o s e to t h e f o r m w h e r e t h e p r o t o n is l o c a l i z e d o n N~, b e c a u s e o f t h e c l o s e s i m i l a r i t y b e t w e e n t h e n . m . r , s p e c t r a o f (21 a n d b e n z a l d e h v d e p h e n y l h y d r a z o n e . M e t a l c o m p l e x e s A s s i g n m e n t s o f t h e L~C r e s o n a n c e s o f t h e c o o r d i n a t e d for- m a z a n s in m e t a l c o m p l e x e s o f f o r n m l a F o N i L ( k = N H ~ . py o r t p p ) w e r e o b t a i n e d in t h e s a m e w a y as t h e a s s i g n m e n t s f o r t h e u n c o o r d i n a t e d f o r m a z a n s a n d bV c o m p a r i s o n w i t h t h o s e p u b - fished ~a~ for m e t a l c o m p l e x e s o f d i h v d r o x v a z o b e n z e n c s .Table !. ~*(' Chemical shifts (ppm rehnivc to TMS) for frcc and con3plcxed forlllaZallS
C o m p o u n d ( ' . ('~: ( ' ~ C'~, ('~ ( ' > ('; ('u C',: (';, (',, ('~1 ('¢" ( ' ~ ( ' q ('1-I~ (',,, C'~ C'~,, C'~ H,Fo 138.3 H2"CI.h-Fo 138.4 t I:t~CI L-Fo 138.3 TI'F ~'' 146.8 F,,)NiNIt,(A) 138.~ 14~. I F,aNiNI 1~( B ) 14(',.2 '" 1(-,0.4 F o N i p y ( A ) 139.0 146.g "CI l~-FoNipy(A) 139.0 146.8 **CH~-FoNipy(A) 139.1 14~.8 FoNipy(B) 146.1'" lfil.6 "CIM-FoNipy(B) 146.11;" 161.h t~('lt~-FoNipy(B) 146. I "~ 161.5 FoNitpp(B) 145.8" 162.9 ~'' "('H~-FoNitpp(B) 145.9" 1 ¢~2.~?" IICIM-FoNitpp(B) 145.7 ~" 162.7 h' FoPdNt]~ 147.1"' 162.9 FoPdpy 146.8'" 163.4 FoPdtpp 146.5'" 163.2 t" FoPtpy 145.6'" 162.7 FoPttpp 145.2'" 163.2 h' 151.7 117.2 131.7 119.2 151.6 117.3 131.5 119.1 151.3 117.2 130.9 llt;.l 117.7 128.3 126.4 117.(I 129.1" 14.8 ~" 128.1 16.9 128.9 1 ~'~. ,"l 128.9 ~ 1 (~. ,"1 12,":.9 ~ 14.6 ~" 128.1 14.(3 ~" 12,'I.(I 14.6 b~ 127.9 15. I"' 128.3 15.1 ~" 128.2 15.1 ~" 128.2 15.9 h' 129.6 14.8 h' 128.9 128.3 19.5 15.8 < 19.7 19.6 19.6 15.9 I" 15.tP ) 15.t) t" 15.9 I', 15.8'" 15.9"' 1¢~.7 h I(~.1 h' 15.5 h~ 128.9 15.7 h~ 15.5 b~ 127.0 115.5 h 15.5 b~ 127.2 115.7 ~'' 129.9 135.7 125.4 124.3 127.6 127.(~ 142.1 114.5 12,~.4 123.3 129.5 135.6 132.7 124.2 12~.3" 136.9 142.1 114.5 128.4" 123.2 20.0 128.7 135.¢~ 135.~ 124.2 127.(, 12¢~.8 14().4 115.() 129.(I 134.() lq. t) 137.1 135.3 12h. l 128.5" 128.3 144.7 112.7 12t;.3 '~ 120.1 177.7 139.9 126.3 124.7 127.2 126.5 14t~.S 117.7 12S.3 126.4 129.(I '~ 14t).3 13().(I 128.2 126.7 12c~.3 151.S 122.< <4. 128.2 123.1 115.3 ~" 144.4"' 137.1 124.(I 128.2 12¢~.1 *' 152.4 122.4 127.3 125.9 ¢' 128.9 148.7 13(I.I 12,'4.2 12(~.7" 12<2 151.1 123.() 12(~.S" 122.0 128.8 '~ 148.9 127.2 128.1 127.4" 13(~.1 151.1 123.(I 127.2" 1213) 2(I.1 12S.~9 ~ 14<<-1.5 d' 120.2 12<'4.2 12¢~.7 126.1 148.~ 'h 122.8 127.5 131. t) ltJ.t~ 115.4 bp 144.8"' 137.1 124.4 c' 127.3 126.1 153.11 124. P" 12¢'~.7 I24.8 115.4 b~ 145.(1"' 134.5 124.4 ~' 12N.() 136.0 152.11 124.0 ~' 126.7 124.7 2(LO 115.4 ~" 144.7"' 137.2 124.0 '' 127.2 12(~.11 15(I.7 124.O ~' 127.2 134.7 19.5 11¢~.7 ~" 145.3" 137.1 124.1 127.3 12¢~.3 15(~.IP 124.5 h~ 126.7 124.N ll(~.ff" 145.3" 134.3 124.1 12N.H 130.1 156.2 hJ 124.(~ h' 126.7 124.8 21).(I I I(~.T" 145.5"' 137.3 124.3 127.4 12¢5.3 153.S h~ 124.3 127.4 134.9 19.7 118.4 ~''-''' 13g.S 125.P' 128.9 12(~.7 ~' 153.N 124.O ~' 12N.(} 12(~.4 ~' 117.8 b' 141.4"' 138.3 124.4 ~ 127.3 125.8 ~' 152.8 124.2 ~~ 12~.9 125.3 e~ 117.5 h' 141.4"' 13S.3 124.6 127.2 12¢~.S g~ 152.8 h, 125.6 h~ I26.(~ 12~.0 ~' 117.4 b ' - ' ' 139.3 124.7 ~'' 127.2" 125.¢V ~- 124.9 ~'' 127.H" 125.9 ~ 117.5 h' 144.7'" 138.8 124.(~ 127.2 12(~.S ~' 15S.3 ~" 125.6 h~ 126.6 126.0 g~
~' -~J A s s i g n m e n t s m a r k e d w i t h file sanlc loller m a v be i n t e r c h a n g e d : ~'~ CouF, Icd w i t h q|:'. o.n.q-,lmg constant m all cases < 7 I lz: " TF'F = 1.3.5- t f i p h c n y l f o r n l a z a n : ~'~ Ct~HL, N: = b e n z a l d e h v d c p h c n y l h y d r a z o r m .
Transition Mct. C h c m . 5, 357-361 (1981)) 1-(2-1 lydr,,+xy :,hcnyl )-3.5-dil+,hcnytft+rrnazan cc, mplcxc:, ,,ff Ni II, Pd t~ and Ptn 359 T h e L~C s i g n a l s o f f r e e a n d c o m p l e x e d ligancl, L, w h e r e f o u n d at t h e p o s i t i o n s e x p e c t e d f r o m l i t e r a t u r e d a t a for p y r i d i n e 1151 a n d t r i p h e n y l p h o s p h i n e ~>' ~71. In t p p t h e t3C sig- n a l s a r e split d u e t o q p - 1 3 C c o u p l i n g . A s t h e r e is a p r o n o u n c e d d i f f e r e n c e in t h e f o r m a z a n r e s o n a n c e s in t h e F o N i L i s o m e r s A a n d B, t h e as y e t u n k n o w n s t r u c t u r e o f t h c p a l l a d i u m a n d p l a t i n u m c o m p l e x e s c a n b e d e f i n i t e l y a s s i g n e d f r o m t h e n . m . r . s p e c t r a . F r o m t h e s e it is c l e a r t h a t t h e p l a t i n u m a n d p a l l a d i u m c o m p l e x e s h a v e t h e f o r m a z a n c o o r d i n a t e d in t h e i s o m e r i c f o r m B [ s t r u c t u r e (4)]• I n f r a r e d spectra N o a t t e m p t h a s b e e n m a d e to a s s i g n f o r m a z a n s k e l e t a l vi- b r a t i o n s in the 4()01)-600 c m -] r e g i o n , as t h e v e r y s t r o n g elec- t r o n d e l o c a l i s a t i o n g i v e s rise to s t r o n g c o u p l i n g o f v i b r a t i o n a l m o d e s . T h i s m a k e s a s s i g n m e n t o f i n d i v i d u a l v i b r a t i o n s u n c e r - t a i n (ts). T h e s t r o n g " ' f i n g e r p r i n t " s i m i l a r i t y in t h e 17()11-600 c m i r e g i o n b e t w e e n t h e i.r. s p e c t r a o f F o P d N H 3 ( p y ) a n d F o P t N H ~ ( p y ) o n t h e o n e h a n d a n d F o N i N H ~ ( p y ) ( B ) o n t h e l 1 6 0 0 1 4 0 0 ~(cm -~) tO T ~ - - 12 0 1 0 0 0 8 0 0 II ,~, L 9(cm -~) 1 6 0 0 1 4 0 0 1 2 0 0 1 0 0 0 8 0 0
',,!2 •::-- :i "'.o r,
k__. , ( % /'/i, ,'/I
i iI
/" ,;]1 ,, ',, : / i ":f/i i I ~11 i J 'iI
I I ii ¸ ,~11 i ¸ ill' ii.lj , II:q i Il
i I "] i ,1[II
i r\' t I / i lt fl I]l I
;t
Figure 2. 1.r. spectra of formazan complcxcs in the 17(IH-h()llcm ~ region.
1"able 2. l.r. bands ''p (cm i) for the nickel complcxcs in the hl)()-2()O cm E region
FoNiN H ~(A) FoNiN H,( B ) Fo Nip5 (A) F(~Nipy(B) FoNitpp(B)
598.3 5 6 3 . 1 ( - 1 , - ) 52~.(} 498( - 2 , 1) 491 sh 482.(1(- 1, - 2 ) 445 435w 416w 31)l( - I, - 34Xw 336( - 2 , -- 299( --3, -- ca. 26()br(-, - 5 ) 248 232 212 583.6 597.3 582.( +, 577.9 571).6 5(~U. 1( 2) 5(',,N.N 5t",3.7 5(,3.1)(- I. - ) 521 .N 5(,3.,'4(-11.5) 552. I 533.11 497. l( - 1 ) 526.7 525+sh ca. 4,'4,<';sh( -5 . - h i 473.8 4Sh.l) 512.(l( - I ) 480.8 4h3.4 472.S 504.9 456.(1( 1. -.) 452w 4 h 5 . 2 ( - I ) 492.2 433 444w c~:. 455',",,, 48(1.(1 41 Ix',,',, 389 4 3 1 ( - I) 44,":(-().5) 399vw 354 ca. 4113w 438 374( 2, - 1 34t~(-41 3 S 4 ( - 5 ) 425w1-1) 345( - 3, - 2 ) 32t~( - h) 3741 - 4 ) 404( - 2) 312 254 31(I 3811(-3) 2 S T + s h ( - , - 4 ) 2 4 2 ( - 4 ) 294 3 5 5 ( - 5 ) 231( - I, - ) 232sh 277```` 297 2115 2h4 2(~7 25(~(-2) 252 22(I 23h+sh 212 '" In parentheses [A'~,('-'Ni), Ai,(15N) or only Ai, C:Ni)].
360 S. Bait, J. Mculdijk and W. E. Renkcma
Table 3. Assignment of M-NH~ vibrational modes :'+ Icm k l in formazan complexes.
Transition Met. Chem. 5. 357-361 (1981])
Compound vINH0 6,j( NIt~} 6,( Nt 10 o(NH0 v( M-N} ~ ( - M N )
FoNiNH~(A) 3362(-8} 3312(-7} 1606(-2} 1257(-7) - 482(-2) 260(-5)
FoNiNH,(B) 3366(-7) 3282( -61 1613(-3) 128{}{ -4} - 486( -6} 287(-4)
FoPdN H, 3362( - 8) 3288{ - 5 ) 1 t~ 17( - 2 ) 1231 ( - 3 } - 446( - 7 ) 249{ - 3)
FoPtNH, 334o( - ,"; ) 324~(-8) 163,'-;(-4) 12NO(-5) 8o3(-3) 445(- I) 231(-2)
;u The symbol notation follows Nakamoto (rcl. 19); the shift observed on I~NFI~ or ":Ni [for 6(-MN)] isotope substitution is given in parenth-
USES.
other hand (see Figure 2 for the ammine compounds) are a further indication that the palladium and platmunl c o m p o u n d s also have the swnmetrical six-membered chelate ring.
Infrared data of the
FoNiL
complexes for the 6{l(I-2()[) cm i region are summarized in Table 2. Assignments have been assisted by the isotope substitution m e t h o d using JSNH.~ and 'aNi. In Table 2 only shifts > 0 . 5 cm-a are recorded. The posi- tion of the metal-ligand vibrations follows from a comparison of a series of F o N i L c o m p l e x e s with varvin,,. ~ L. Due to the 15NH 3 substitution, the ftmdamental M - N I t ~ modes <l'*' can localized without difficulty and are given in Table 3. The Ni-py modes were found at the predicted cu~ positions. Table 4 con- tains the assignments for the nickel-ligand stretching vibra- tions. The metal-ligand stretching and bending vibrations M-Nft~ show the expected decrease on going from nickel to platinum.Experimental
Preparations
The tridentate formazans were prepared following the pro- cedt, re described bv Wizinger'elL Commercially available 1,3,5-triphenylformazan (Fluka, purum) was recrvstallized from M e O H .
Ammine/ l-(2-hydro.vypheto.l)-3,5-dqgteny!l?mm+zumm,/-
nickel(ll) (isomer A
With vigorous stirring. Ni(CIOa)_~ . t~ t b O (Fh, ka. puruna, p.a.) (12 g) was added to a filtered solution of formazan
12)
(1{I g) hi a mixture of M e , C O (1(]0 cm ~) and concentrated aqueous NH3 (120 cm~). A f t e r two min the solution was ill-
tered and poured o n t o p o w d e r e d ice (2 kg). A f t e r one day the precipitate formed was filtered off and dried in vacuo o v e r K O H . The product was purified by column c h r o m a t o g r a p h y o v e r silica gel (Merck, Kieselgel
60,
grain sizes 0.063 to 0.200 mm) using CH2CI2 as the elutant. Yield 40%.Pvridine/ l-(2-hydroxyphenyl)-3,5-diphenyl/brnmzanato/-
niekel(ll) (isomer A)
This complex was prepared from the a m m i n e complex bv adding pyridme (20 cm 3) to a solution of the a m m i n e complex ( 10 g) in CIf2CI_+ (200 cn¢). A f t e r 30 rain stirring at 35 ° E t O H (50 cm 3) was added. The complex was precipitated by eva- poration of the C H , C h from the mixed solvent. Purification was effected by c h r o m a t o g r a p h y as described above. Yield 90%.
Ammine-. pyridim'- and lrifflteltylpttosphine/l-(2-10"drox.v-
lgtenylJ-3.5-diplteto'!lbrmazamtto/niekelUl) (isomers
B)
Ni(CIO4)e • 6 H+O (5 g) dissolved in a minimum amount
of
EtOH was added to a hot solution of
(2) (5 g) in E t O I t
(750cm3L After refluxing for 15 rain concentrated aqueous
NII~ (25 cm~), pyridme (10 cm~), or Ph~P (4 g). respectively.
were added. A f t e r cooling the precipitate formed was filtered off and recrystallized from E t O H , Yield 40-71F;-.
Type A and B c o m p l e x e s containing "-'Ni were prepared on a micro scale following the procedures described above, using <Ni(NO3)2 (from metallic 'eNi, Rohstoff. DiisseMorf). The methyl substituted c o m p o u n d s of isomer type A and B were obtained using the procedures outlined above for their parent conlpounds.
Table4. Mctal-ligand stretching vibramns (cm
i)
in FoNiX cum- plcxcs'"Complex Ni-X Ni-N~ Ni-N, Ni-() Ni-N~ Ni-N, FoNiNHdA) 4,'42 391 'u 49,'.4 336"'
299;"
FoNiNH~(B) 486 FoNipy(A) 242 FoNipy( 13 ) FoNitpp( 13 ) 374 456 345 349 497.1 329 256 3~4 465.2"' 374 43U ' 404 ''~ 512.11'" 381P' 448"' 355"" 425"'., Definite assignment could not bc made for these vibrations.
Ammine-, pyridim'- am/ trilgwnylplu;slgmze/l-(2-1tydrox)'-
phenyl~-3.5-dip/lenyllbrmazamm~/l~alladitmt(ll)
Hsomer B)
To a solution of formazan
(21
( 4 g ) in heated E t O H (100 cm~), was added one equivalent of Pd(NOO+, • 2 H : O (Drijfllout. A m s t e r d a m ) dissolved in a minimuna amount of H~O during 30 rain. To this solution concentrated aqt, eous NH~ (25 cn¢), pyridine (10cm3). or Ph~P (3.6 g), respectively. were added. The tpp complex crystallized pure from this mix- ture: yield 70%. For the other c o m p o u n d s the reaction mix- ture was then filtered at elevated t e m p e r a t u r e and the filtrate concentrated under reduced pressure to 200 cm ~. A f t e r cool- ing, the precipitate formed was filtered off and dried in w+cuo over K O H . Column c h r o m a t o g r a p h y as described above was again used for purification, Yield 3(H>~ - .The tSNtt.~ substituted c o m p o u n d s of nickel and palladium were obtained from their parent NH~ c o m p o u n d s by treating these with a 2()-fold excess of tSNH.~ ( R o h s t o f f , Diisseldorf),
Transition Met. Chem. 5, 357-361 ( 1 9 8 0 ) 1-( 2-Hydroxyphcnyl I-3,5-diphenylformazan complexes of Ni n, Pd" and Pt n
Table 5. Analytical data for the formazan and mt2tzll-fornlaz~.lll coml"~lcxcs
361
Compound Found (Calcd.)~;
C H N (.) P Metal H2"CH3-Fo 72.7(72.7) 5.64(5.5) H21~CH~-Fo 72.5(72.7) 5.46(5.5) FoNiNH3(A) 58.3(58.5) 4.70(4.4) "CH3-FoNiNH3(A) I~CH)-FoNiNH~(A) FoNiNH3(B) I~CH~-FoNiNH~(B) FoNipy(A) 63.6(63.75) 4,51(4.2) "CH3-FoNipy(A) I~CH~-Fo-Nipy(A) FoNipy(B) 63.6(63.75) 4.07(4.2) "CH3-FoNipy(B) ~CH3-FoNipy(B) FoNitpp(B) 69.9(69.95) 4.70(4.O) "CH~-FoNitpp(B ) I~CH~-FoNiIpp(B) FoPdNH~ 52.(1(52. I ) 3.9(1(3.9) FoPdpy 57.4(57.7) 3,86(3.81 FoPdtpp 64.7(65.11 4.35(4.31 FoPtNH~ 43.4(43.35) 3.25(3.3) FoPtpy 48.8(49.fl) 3.37(3.25) FoPttpp 57.5(57.6) 3.72(3.81 18.(I 18.fl) 15.5 15.5) 15.5 (15.5) S.83 (8.91 15.9 ( 16.111 13.9 (14.0) 8.(18 (8.2t 13.4 (13.3) 11.9 (11.9) 7.17 (7.31 4.4 (4.1) - 150 (15.(15) - 145 114.5) - 1 4 . 4 ( 1 4 . 5 1 - 1 5 . 2 ( 1 5 . 1 1 5 ) - 1 4 . 5 ( 1 4 . 5 ) - 1 3 . 1 ( 1 3 . ( 1 1 - 1 2 . 6 ( 1 2 . 6 1 - 1 2 . 8 ( 1 2 . 6 ) 3.43(3.5) - 13,1 (13.11) - 12.5 112.6) - 1 2 7 ( 1 2 . ~ 1 2.39(2.51 4.8fl(4.9) 9.35 (9.2) ~.fl (9.o) 9.1 (9.0) 3.~2(3.~5) 3.17(3.21 2.o1(2.31 4.3214.5t 1.S9(2.1) 3.9414.01 3 - 2 137.fl5) 32.9 (33.15)
Pvridim'- and triphenylplmspldne/l-(2-tLvdroxyl)tu'n.vl)-3,5- dipheny(lbrmazanato/phttimun(ll) (isomer B)
T h e s e c o m p l e x e s w e r e p r e p a r e d as d e s c r i b e d for their pal- ladium a n a l o g u e s , with the e x c e p t i o n that K_,PtCI4 was used and the c o m p l e x e s w e r e isolated from the reaction mixture by e v a p o r a t i o n o f 90% o f the solvent. Yield 2(1%.
A m m i n e / l-(2-hydroxyphenyl)-3,5-dipheny(lbrmazamlto/- platinum(ll) (isomer B)
This c o m p l e x was p r e p a r e d by m e t a t h e s i s from t h e
pyridine c o m p l e x by dissolving the starting material (1 g) in D M S O ( 5 0 c m 3 ) , to which c o n c e n t r a t e d a q u e o u s NH~ (10 cm 3) was a d d e d . A f t e r 30 min refluxing, the solution was c o o l e d and the a m m i n e c o m p l e x p r e c i p i t a t e d by slow dropwise a d d i t i o n of H 2 0 . Yield 9 5 % .
T h e LSNH3 c o m p o u n d was o b t a i n e d in the same way using two t r e a t m e n t s with a 20-fold excess of tSNH.~.
Ana@ses
Analytical data for the f o r m a z a n s and the metal c o m p l e x e s p r e p a r e d are s u m m a r i z e d in Table 5. The e l e m e n t a l analyses w e r e p e r f o r m e d u n d e r supervision of Mr. W. J, Buis at t h e
Micro-Analytical D e p a r t m e n t o f the Institute for Organic C h e m i s t r y , T N O , U t r e c h t , T h e N e t h e r l a n d s .
Spectra
t3C n . m . r , s p e c t r a w e r e r e c o r d e d with a Varian XL-10(I FF S p e c t r o m e t e r in CH2CI2 or CI-ICI3 as solvent. T h e s p e c t r o m e - ter was locked on CDCI3 ( M e r c k , Uvasol) c o n t a i n e d m a coa- xial inner cell. C h e m i c a l shifts were m e a s u r e d relative to the solvent and c o n v e r t e d to T M S as r e f e r e n c e . The low solubility of FoPtNH3 p r e v e n t e d the r e c o r d i n g of a s p e c t r u m for this c o m p l e x .
l.r. s p e c t r a were r e c o r d e d with a P e r k i n - E l m e r 580-B (4000-200 cm - I ) o r a B e c k m a n 1R-720 F o u r i e r S p e c t r o m e t e r , using p r e s s e d Csl discs. Similar spectra were o b t a i n e d using
nujol or h e x a c h l o r o b u t a d i e n e lnnlls s a n d w i c h e d b e t ~ e e n KBr discs for the 4{}{1{I-6{}{) cm -1 region, nu,iol mulls b e t w c e n p o l y e t h y l e n e windov,,s for the 05{}-21}1} c m - j region and
p r e s s e d p o l y e t h y l e n e discs for the 41111-11)(I cm i region. U.v. and vis a b s o r p t i o n spectra were r e c o r d e d with a Beck- man A c t a C llI S p e c t r o p h o t o m e t e r .
A c k n o w l e d g e m e n t
The a u t h o r s are grateful to Mrs. J. B r e m a n , J. v. d. Giessen and J. M i t t e n d o r f for their wfluable help in the e x p e r i m e n t a l part.
R e f e r e n c e s
,1~ A. M. A. Vcrwey and S. Bali. hlorg. (71inl. Acta. 4. 351 (It)70).- c2~ S. Ball and W. E. Renkema, htorg. (71inr Acta, 22. 161 (1977).- ~ W . E. Renkema, Dissertation, Amsterdam ( 1 9 7 5 ) . - '~' W. E. Rcnkcma, ('. N. Lute and C. H. Stare. Acta ()'.vstallogr., B35. 75 (1979). - ~) J. Meuldijk, Dissertation. Amsterdam (1979). - ~''~ S. Bah and J. Mcu[dijk. Z. Natuffor~ch.. 34h. 843 (1979). - ,7, S. Bait. W. E. Renkema, C. wm Capellevccn and C. H. Slam. J. Morg. Nucl. Chem., 38, 459 (1976). - t,',Jj. F. van Baar, K. Vriczc and D. J. Stufkens, J. Orgunometal. Chem.. 81. 247 ( 19741. - c,, K. S. Dhami and J. B. Stothcrs, Can. J. Chem.. 43. 479 (1965L - '"" Y. Nakai and F. Yamada, Or~,,. Magn. Res.. 1l, 6117 (1978).
~J E. Brcitmaicr and W Voelter. re(, NMR Spectrosc(q)y, Vcrlag Chcmie, Wcinheim, 1974, p. 171, - t~:~ p. B. Fischcr, B. L. Kaul and H, Zollinger, Heh'. Chim. Acta, 51, 1449 { 1968). ii;, G. Arnold and C. Schiclc, Spectrochinr Acta. 25A. 685 (196t)). -~la. p. S. Prcgosin and E. Steincr, Heh,. Chim. Acta, 02, 62 {1979). - q>P M. A. M. Mecsters, D. J. Stufkens and K. Vriezc, lnortL (Trim, Act& 15, 137 (1975). -~1,, Rcf. 11, p. 106, 107. -,i;~ j. F. van Baar. K. Vriezc and D. J. Stufkens, J. Orffanometal. (7win., 85. 24t~ (1975). - ~lsb p. R. Johnson and D. A. Thornton, Spectrosc. Lett.. 7, 293 (1974). - ~"'~ K. Nakamoto, In])'ared and Ralnan Spectra of Inorganic and Coordina- tion Conq~ounds. Wile',. New York. 197,'-;. p. 199, c,,, R. J. H. Clark and ('. S. Williams, lnor£,. ('hem.. 4, 35(I (1905L
~2u R. Wizingcr, HeN, Chim Acta, ,:/2, 901 (1949).
